emulsion polymer particles comprising from 25 to 45 wt % polymerized residues of at least one C3-C6 carboxylic acid monomer and from 0.1 to 2 wt % polymerized residues of at least one crosslinker, wherein the particles have a tg which occurs over a range of at least 60° C.
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1. emulsion polymer particles comprising from 29 to 41 wt % polymerized residues of at least one of acrylic acid and methacrylic acid, from 58 to 70 wt % polymerized residues of at least one C1-C8 alkyl (meth)acrylate and from 0.1 to 1.5 wt % polymerized residues of at least one crosslinker, wherein the particles have a tg which occurs over a range of at least 60° C.
4. A method for producing the emulsion polymer particles by steps of: (a) providing a first monomer mixture comprising from 15 to 28 wt % of at least one C3-C6 carboxylic acid monomer; (b) providing a second monomer mixture comprising from 9 to 17 wt % of at least one C3-C6 carboxylic acid monomer; and (c) adding the first monomer mixture to a polymerization reactor while simultaneously adding the second monomer mixture to the first monomer mixture; wherein weight percentages are based on total weight of the first and second monomer mixtures.
2. The polymer particles of
3. The polymer particles of
5. The method of
6. The method of
7. The method of
8. The method of
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This invention generally relates to alkaline-swellable emulsion polymers made using a power feed of monomers.
Polymers made using power feed of monomers are known. For example, U.S. Pat. No. 3,804,881 discloses polymers made using this process. However, the alkaline-swellable polymers disclosed in the present application, which are useful as rheology modifiers, are not known.
The problem solved by the present invention is to provide additional alkaline-swellable polymers for use as rheology modifiers.
The present invention is directed to emulsion polymer particles comprising from 25 to 45 wt % polymerized residues of at least one C3-C6 carboxylic acid monomer and from 0.1 to 2 wt % polymerized residues of at least one crosslinker, wherein the particles have a Tg which occurs over a range of at least 60° C.
The present invention is further directed to a method for producing the emulsion polymer particles by steps of: (a) providing a first monomer mixture comprising from 15 to 28 wt % of at least one C3-C6 carboxylic acid monomer; (b) providing a second monomer mixture comprising from 9 to 17 wt % of at least one C3-C6 carboxylic acid monomer; and (c) adding the first monomer mixture to a polymerization reactor while simultaneously adding the second monomer mixture to the first monomer mixture; wherein weight percentages are based on total weight of the first and second monomer mixtures.
All percentages are weight percentages (wt %), all fractions are by weight and all temperatures are in ° C., unless otherwise indicated. Percentages of polymerized monomer residues in polymers are based on the entire weight of the solid polymer and percentages of monomers are based on total monomer weight. Measurements made at “room temperature” (room temp.) were made at 20-25° C. Any term containing parentheses refers, alternatively, to the whole term as if no parentheses were present and the term without them, and combinations of each alternative. Thus, the term “(meth)acrylic” refers to any of acrylic, methacrylic, and mixtures thereof. A “C3-C6 carboxylic acid monomer” is a mono-ethylenically unsaturated compound having one or two carboxylic acid groups, e.g., (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, crotonic acid, etc. Preferably, the acid monomer has three or four carbon atoms, preferably one carboxylic acid group, preferably (meth)acrylic acid, preferably methacrylic acid (MAA). Alkyl groups are saturated hydrocarbyl groups which may be straight or branched.
As used herein, unless otherwise indicated, the phrase “measured glass transition temperature” or “measured Tg” of a copolymer refers to a measured Tg, determined by modulated differential scanning calorimetry (MDSC) scanning from −150° C. to 150° C. while ramping temperature in a given sinusoidal modulation (oscillation) pattern overlaid on a conventional linear heating ramp at a ramp rate of 2.00° C./min to 150.00° C., taking the mid-point in the heat flow versus temperature transition as the Tg value. As used herein, the term “broad measured glass transition temperature (broad measured Tg)” refers to an MDSC glass transition wherein either the onset or final temperature of the recorded temperature curve are poorly defined. An example of a polymer having a broad measured Tg is a powerfeed emulsion copolymer. Preferably, the Tg of the particles occurs over a range of at least 65° C., preferably at least 70° C., preferably at least 75° C., preferably at least 80° C.
Crosslinkers are monomers having two or more non-conjugated ethylenically unsaturated groups. Preferred crosslinkers include, e.g., di- or tri-allyl ethers and di- or tri-(meth)acrylyl esters of diols or polyols (e.g., trimethylolpropane diallyl ether (TMPDAE) and trimethylolpropane trimethacrylate (TMPTMA)), di- or tri-allyl esters of di- or tri-acids, allyl (meth)acrylate, divinyl sulfone, triallyl phosphate, divinylaromatics (e.g., divinylbenzene). Preferably, the crosslinker has a molecular weight no greater than 800, preferably no greater than 700, preferably no greater than 600, preferably no greater than 500, preferably no greater than 400. Preferably, the molecular weight of the crosslinker divided by the number of ethylenically unsaturated groups is no greater than 150, preferably no greater than 140, preferably no greater than 130; preferably at least 50, preferably at least 65.
Preferably, the polymer particle is an acrylic polymer, i.e., one having at least 70 wt % polymerized residues of acrylic monomers, preferably at least 80 wt %, preferably at least 90 wt %, preferably at least 95 wt %, preferably at least 98 wt %, preferably at least 99 wt %. Acrylic monomers include (meth)acrylic acids and their C1-C22 alkyl or hydroxyalkyl esters; crotonic acid, itaconic acid, fumaric acid, maleic acid, maleic anhydride, (meth)acrylamides, (meth)acrylonitrile and alkyl or hydroxyalkyl esters of crotonic acid, itaconic acid, fumaric acid or maleic acid. The acrylic polymer may also comprise other polymerized monomer residues including, e.g., non-ionic (meth)acrylate esters, cationic monomers, monounsaturated dicarboxylates, vinyl esters of C1-C22 alkyl carboxylic acids, vinyl amides (including, e.g., N-vinylpyrrolidone), sulfonated acrylic monomers, vinyl sulfonic acid, vinyl halides, phosphorus-containing monomers, heterocyclic monomers, styrene and substituted styrenes. Preferably, the polymer contains no more than 3 wt % sulfur- or phosphorus-containing monomers, preferably no more than 2 wt %, preferably no more than 1 wt %, preferably no more than 0.5 wt %, preferably no more than 0.2 wt %.
Preferably, the polymer particles also comprise 54 to 74 wt % polymerized residues of at least one C1-C12 alkyl(meth)acrylate; preferably, at least 56 wt %, preferably at least 58 wt %, preferably at least 60 wt %, preferably at least 62 wt %; preferably no more than 72 wt %, preferably no more than 70 wt %, preferably no more than 68 wt % Preferably, the C1-C12 alkyl(meth)acrylate is limited to a C1-C8 alkyl(meth)acrylate, preferably a C2-C8 alkyl (meth)acrylate; preferably the C1-C12 alkyl(meth)acrylate is limited to a C1-C12 alkyl acrylate, preferably a C1-C8 alkyl acrylate, preferably a C2-C8 alkyl acrylate. Preferably the polymer particles comprise at least 27 wt % polymerized residues of at least one C3-C6 carboxylic acid monomer, preferably at least 29 wt %, preferably at least 31 wt %, preferably at least 33 wt %; preferably no more than 43 wt %, preferably no more than 41 wt %, preferably no more than 39 wt %, preferably no more than 37 wt %. Preferably the polymer particles comprise at least 0.3 wt % polymerized residues of at least one crosslinker, preferably at least 0.4 wt %, preferably at least 0.5 wt %; preferably no more than 2.5 wt %, preferably no more than 2 wt %, preferably no more than 1.5 wt %, preferably no more than 1.2 wt %, preferably no more than 1 wt %, preferably no more than 0.9 wt %, preferably no more than 0.8 wt %.
Preferably, the polymer particles comprise polymerized residues of a lipophilic monomer having the structure H2C═C(R)C(O)X(CH2CH2O)n(CH(R′)CH2O)mR″, wherein X is O or NH, R is hydrogen or methyl, R′ is methyl or ethyl; R″ is C8-C22 alkyl, C8-C16 alkylphenyl or C13-C36 aralkylphenyl; n is an average number from 6-100 and m is an average number from 0-50, provided that n≧m and m+n is 6-100. Preferably, X is O. Preferably, the polymer particles comprise from 0.2 to 10 wt % polymerized residues of monomers of structure H2C═C(R)C(O)X(CH2CH2O)n(CH(R′)CH2O)mR″, preferably from 0.3 to 8 wt %, preferably from 0.5 to 5 wt %, preferably from 0.5 to 4 wt %, preferably from 1 to 4 wt %. Preferably, R″ is C8-C22 alkyl, preferably C10-C22 alkyl, preferably C12-C20 alkyl. Preferably, n is 15-30 and m is 0-5; preferably n is 18-25 and m is 0-3; preferably n is 18-25 and m is 0-2; preferably R′ is methyl. Preferably, R is methyl. Preferably, R″ is C12-C22 alkyl, n is 15-30 and m is 0-5; preferably, R″ is C12-C22 alkyl, n is 18-25, m is 0-3 and R is methyl.
Preferably, the polymer particles are provided as an aqueous composition containing the polymer as discrete particles dispersed in an aqueous medium, i.e., a polymer latex. In this aqueous dispersion, the average particle diameter of the polymer particles preferably is in the range from 50 to 2000 nm, preferably from 100 to 1000 nm, preferably from 150 to 800 nm. The level of polymer particles in the aqueous dispersion is typically in the range of from 15 to 60 wt %, preferably 25 to 50 wt %, based on the weight of the aqueous dispersion. Preferably, the percentage of crosslinker and the acid monomer content increase continuously from particle centers to particle surfaces.
In describing the method of this invention, percentages of monomers are based on the total monomer weight. Preferably, the first monomer mixture further comprises from 54 to 74 wt % polymerized residues of at least one C1-C12 alkyl(meth)acrylate; preferably, at least 56 wt %, preferably at least 58 wt %, preferably at least 60 wt %, preferably at least 62 wt %; preferably no more than 72 wt %, preferably no more than 70 wt %, preferably no more than 68 wt %. Preferably, the C1-C12 alkyl(meth)acrylate is limited to a C1-C8 alkyl(meth)acrylate, preferably a C2-C8 alkyl(meth)acrylate; preferably the C1-C12 alkyl(meth)acrylate is limited to a C1-C12 alkyl acrylate, preferably a C1-C8 alkyl acrylate, preferably a C2-C8 alkyl acrylate. Preferably the first monomer mixture comprises at least 17 wt % of at least one C3-C6 carboxylic acid monomer, preferably at least 18 wt %, preferably at least 19 wt %, preferably at least 20 wt %; preferably no more than 25 wt %, preferably no more than 24 wt %, preferably no more than 23 wt %, preferably no more than 22 wt %. Preferably, the first monomer mixture further comprises from 0.1 to 2 wt % polymerized residues of at least one crosslinker. Preferably, the first monomer mixture comprises at least 0.2 wt % of at least one crosslinker, preferably at least 0.3 wt %, preferably at least 0.4 wt %, preferably at least 0.5 wt %; preferably no more than 2.5 wt %, preferably no more than 2 wt %, preferably no more than 1.5 wt %, preferably no more than 1.2 wt %, preferably no more than 1 wt %, preferably no more than 0.9 wt %, preferably no more than 0.8 wt %.
Preferably, the second monomer mixture comprises at least 10 wt % of at least one C3-C6 carboxylic acid monomer, preferably at least 11 wt %, preferably at least 12 wt %; preferably no more than 16 wt %, preferably no more than 15 wt %, preferably no more than 14 wt %. Preferably, the second monomer mixture further comprises from 0.1 to 2 wt % polymerized residues of at least one crosslinker. Preferably, the second monomer mixture comprises at least 0.2 wt % of at least one crosslinker, preferably at least 0.3 wt %, preferably at least 0.4 wt %, preferably at least 0.5 wt %; preferably no more than 2.5 wt %, preferably no more than 2 wt %, preferably no more than 1.5 wt %, preferably no more than 1.2 wt %, preferably no more than 1 wt %, preferably no more than 0.9 wt %, preferably no more than 0.8 wt %. Preferably, the second monomer mixture further comprises up to 15 wt % of monomers which are not crosslinkers, preferably up to 10 wt %, preferably up to 8 wt %. Preferably, the monomers in the second monomer mixture comprise no more than 5 wt % C1-C12 alkyl(meth)acrylate(s), preferably no more than 3 wt %, preferably no more than 2 wt %, preferably no more than 1 wt %, preferably no more than 0.5 wt %, preferably no more than 0.2 wt %.
Preferably, the first monomer mixture comprises a lipophilic monomer having the structure H2C═C(R)C(O)X(CH2CH2O)n(CH(R′)CH2O)mR″, wherein X is O or NH, R is hydrogen or methyl, R′ is methyl or ethyl; R″ is C8-C22 alkyl, C8-C16 alkylphenyl or C13-C36 aralkylphenyl; n is an average number from 6-100 and m is an average number from 0-50, provided that n≧m and m+n is 6-100. Preferably, X is O. Preferably, the first monomer mixture comprises from 0.2 to 10 wt % of monomers of structure H2C═C(R)C(O)X(CH2CH2O)n(CH(R′)CH2O)mR″, preferably from 0.3 to 8 wt %, preferably from 0.5 to 5 wt %, preferably from 0.5 to 4 wt %, preferably from 1 to 4 wt %. Preferably, R″ is C8-C22 alkyl, preferably C10-C22 alkyl, preferably C12-C20 alkyl. Preferably, n is 15-30 and m is 0-5; preferably n is 18-25 and m is 0-3; preferably n is 18-25 and m is 0-2; preferably R′ is methyl. Preferably, R is methyl. Preferably, R″ is C10-C22 alkyl, n is 15-30 and m is 0-5; preferably, R″ is C12-C22 alkyl, n is 18-25, m is 0-3 and R is methyl.
Preferably, the first monomer mixture comprises a nonionic water-soluble monomer, preferably having the structure H2C═C(R)C(O)X(CH2CH2O)n(CH(R′)CH2O)mR″, wherein X is O or NH, R is hydrogen or methyl, R′ is methyl or ethyl; R″ is methyl or ethyl; n is an average number from 6-100 and m is an average number from 0-50, provided that n≧m and m+n is 6-100. Preferably, X is O. Preferably, the first monomer mixture comprises from 0.2 to 10 wt % of monomers of structure H2C═C(R)C(O)X(CH2CH2O)n(CH(R′)CH2O)mR″, preferably from 0.5 to 8 wt %, preferably from 1 to 7 wt %, preferably from 2 to 7 wt %, preferably from 3 to 7 wt %. Preferably, R″ is methyl. Preferably, n is 15-30 and m is 0-5; preferably n is 18-25 and m is 0-3; preferably n is 18-25 and m is 0-2; preferably R′ is methyl. Preferably, R is methyl. Preferably, R″ is methyl, n is 15-30 and m is 0-5; preferably, R″ is methyl, n is 18-25, m is 0-3 and R is methyl. Other preferred nonionic water-soluble monomers include acrylamide, N-methyl or -ethyl acrylamides, N,N-dimethyl or -diethyl acrylamides, polyethylene glycol (meth)acrylate N-vinylacetamide, N-methyl-N-vinylacetamide, N-vinylformamide, N-methyl-N-vinylformamide, N-vinyl lactams hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and mixtures thereof. An especially preferred nonionic water-soluble monomer is methoxy-poly(ethylene glycol) monomethacrylate.
Preferably less than 10 wt % of the monomers is in the polymerization reactor prior to addition of the first monomer mixture, preferably less than 7 wt %, preferably less than 5 wt %, preferably less than 3 wt %, preferably less than 2 wt %, preferably less than 1 wt %. Preferably, the monomers are added to the reactor over a period of time from 60 to 240 minutes, preferably from 80 to 160 minutes, preferably 90 to 150 minutes. Preferably the time of addition of the second monomer mixture to the first monomer mixture is from 50 to 120% of the time of addition of the first monomer mixture to the polymerization reactor, preferably from 75 to 100%, preferably from 90 to 100%. Preferably, addition of the second monomer mixture to the first monomer mixture begins no later than addition of the first monomer mixture to the polymerization reactor, preferably at the same time.
Typical aqueous emulsion polymerization techniques are suitable for use in the method of this invention. Aqueous emulsion polymerization processes typically are conducted in an aqueous reaction mixture, which contains at least one monomer and various synthesis adjuvants such as the free radical sources, buffers, and reductants in an aqueous reaction medium. A chain transfer agent may used to limit molecular weight, preferably a mercaptan, preferably a C8-C12 alkyl mercaptan. The aqueous reaction medium is the continuous fluid phase of the aqueous reaction mixture and contains greater than 50 wt % water and optionally one or more water miscible solvents, based on the weight of the aqueous reaction medium. Suitable water miscible solvents include methanol, ethanol, propanol, acetone, ethylene glycol ethyl ethers, propylene glycol propyl ethers, and diacetone alcohol. Preferably, the aqueous reaction medium contains at least 90 wt % water, preferably at least 95 wt % water, preferably at least 98 wt % water, based on the weight of the aqueous reaction medium.
The emulsion polymer particles of this invention are useful in a variety of thickened aqueous formulations as described above, including body washes, shampoos, personal care cleansers; liquid soap (e.g., liquid hand soap), cleaning formulations for fabric (e.g., laundry detergent), dishes, and hard surfaces; liquid auto-dish detergent, manual dish detergent, spot-pretreaters, oven cleaners, and glass/window cleaners, conditioners (e.g., hair and skin), two-part hair dyes, hair gels; hair-styling cream, paste or gum; mousses, permanent waving formulations, tanning lotions, sunscreens and skin lotions. The polymer also is useful as an emulsifier, e.g., in surfactant-free systems (e.g., creams or lotions). A formulation thickened with the polymer particles can be used to suspend beads, silicones, silica, emollient oils, organic and inorganic uv filters and abrasives. The polymer particles can be used in combination with other rheology modifiers. When the particles are swollen through contact with alkali it often is not possible to distinguish individual particles in the gel-like system which is formed.
A thickened aqueous formulation contains from 0.1 to 5 wt % of the polymer particles, calculated on a polymer solids basis relative to the entire weight of the aqueous formulation. Preferably, a thickened aqueous formulation contains at least 0.3 wt % of the polymer particles, preferably at least 0.5 wt %, preferably at least 0.7 wt %, preferably at least 0.9 wt %, preferably at least 1.1 wt %, preferably at least 1.3 wt %, preferably at least 1.5 wt %. Preferably, a thickened aqueous formulation contains no more than 4 wt % of the polymer particles, preferably no more than 3 wt %, preferably no more than 2.5 wt %, preferably no more than 2 wt %. Preferably, the thickened aqueous composition also contains at least one surfactant, preferably at least two surfactants. Preferred anionic surfactants for use in the practice of the invention may be selected from the C8 to C18 fatty acids or their water soluble salts, water soluble sulfates or ether sulfates of C8 to C18 alcohols, sulfonated alkylaryl compounds such as, for example, dodecylbenzene sulfonate, alkylphenoxy polyethoxy ethanols, for example with C7 to C18 alkyl groups and 9 to 40 or more oxyethylene units, ethylene oxide derivatives of long chain carboxylic acids, for example of lauric, myristic, palmitic or oleic acids, ethylene oxide derivatives of long chain alcohols, for example of lauryl or cetyl alcohols, alkanolamides and polyglucosides, for example the alkyl polyglucosides, and surfactants derived from amino acids, e.g. glutamates. Especially preferred surfactants include, e.g., sodium laureth sulfate (SLES) and cocamidopropyl betaine (CAPB). Preferably the total amount of surfactants in the aqueous composition is from 5 wt % to 30 wt %; preferably at least 8 wt %, preferably at least 10 wt %, preferably at least 12 wt %; preferably no more than 25 wt %, preferably no more than 22 wt %, preferably no more than 20 wt %. Preferably, the pH of the thickened aqueous composition is from 3 to 12, preferably from 3.5 to 10, preferably from 3.5 to 8, preferably from 4 to 7.
Preferably, the polymer particles described in this invention provide clarity and suspension properties for the thickened aqueous composition, i.e., turbidity of the sample is less than 50 NTU, using specifications in U.S. Environmental Protection Agency method 180.1 (Nephelometric Method). Suspending refers to the even dispersion of particulate or solid material, liquid material, or air throughout the continuous phase of the formulation. Failure of suspension is marked by phase separation of the dispersed material from the continuous phase under a range of storage temperature conditions.
A particular aqueous composition in which the polymer of this invention is useful is a body wash. Typical components of a body wash, in addition to the polymer thickener and surfactant mentioned previously, include sufficient base or acid to attain a pH of 4-7, preferably 4.5-6.8, preferably 4.5 to 5.5, preferably 5-6.6; and optional ingredients, including silicones, pearlizing agents, vitamins, oils, fragrances, dyes, biocides, and insoluble beads made from a variety of materials, including polyolefins, e.g., polyethylene and polystyrene; gelatin; mica; encapsulated oil or vitamin beads; and Jojoba wax beads. Preferably, the amount of beads is from 0.1% to 2%, more preferably from 0.2% to 1%. Preferably, the average radius of the beads is from 0.1 mm to 10 mm. Typically, the surfactant used is a mixture of an anionic surfactant and an amphoteric surfactant, preferably from 8% to 16% of an anionic surfactant and from 1% to 5% of an amphoteric surfactant.
A second particular aqueous composition in which the polymer of this invention is useful is a shampoo. Typical components of a conditioning shampoo, in addition to the polymer thickener and surfactant mentioned previously, include sufficient base to attain a pH of 4-7, preferably 4-6, preferably 4.7-7.0. One particular embodiment of the invention is a conditioning shampoo containing a dispersed silicone, and optional ingredients, including pearlizing agents and zinc pyrithione or other anti-dandruff agents.
A third aqueous composition in which the polymer of this invention is useful is a hard surface cleaner. Typical components of a hard surface cleaner in addition to the polymer thickener and surfactant mentioned previously, include sufficient base to achieve a pH of 9-12, and optional ingredients including solvents, salts, fragrances, and dyes.
Preferably, a thickened aqueous composition is produced by neutralizing the emulsion polymer to a pH in the range from 6.5 to 8, preferably from 7 to 7.5, preferably from 7 to 7.5; and then acidifying to a pH in the range from 4 to 6, preferably from 4.5 to 5.5, preferably from 4.8 to 5.3. Suitable bases to neutralize the formulation include mineral bases such as sodium hydroxide and potassium hydroxide; ammonium hydroxide, and organic bases such as mono-, di- or tri-ethanolamine; preferably alkali metal hydroxides; preferably sodium or potassium hydroxide; preferably sodium hydroxide. Mixtures of bases may be used. Suitable acids to acidify the formulation include mineral acids such as hydrochloric acid, phosphoric acid, and sulfuric acid, and organic acids such as acetic acid; preferably carboxylic acids; preferably citric acid. Mixtures of acids may be used.
The composition of the present invention optionally may include other ingredients, e.g., salts, co-rheology modifiers (e.g. LAPONITE clay, cellulosics, carrageenan, xanthan, PEG-150 distearate (ACULYN 60 rheology modifier), PEG-150 pentaerythrityl tetrastearate, other associative or non-associative acrylic rheology modifiers such as acrylates copolymer, derivatives of acrylates copolymer, ACULYN 33 rheology modifier, ACULYN 22 rheology modifier, ACULYN 28 rheology modifier, Acrylates/Beheneth-25 Methacrylate Copolymer, derivatives of Acrylates/Beheneth-25 Methacrylate Copolymer, and ACULYN 88 rheology modifier, CARBOPOL Aqua-SF1, CARBOPOL Aqua 30, and CARBOPOL Ultrez-21, other acrylic or urethane polymers like ACULYN 44 rheology modifier or ACULYN 46 rheology modifier, organic or inorganic particles (including, for example, abrasives, beads, mica, encapsulated oil beads), silicones, pearlizing agents, dispersed liquids, dispersants, soluble or dispersed biocides, vitamins, humectants, enzymes, bleach, emollient, fragrance, dyes, thioglycolic acid, UVA and UVB absorbers, infrared absorbers, etc. Insoluble materials which may be suspended in the aqueous composition include clay, beads, wax, gelatin and other particulate materials.
In the following examples, the following terms and test procedures are used:
To a 3-liter, 4-necked round bottom flask equipped with a mechanical stirrer, thermocouple, condenser and nitrogen sparge was added 729 μm of deionized water and 2 μm of sodium lauryl sulfate. The reactor was purged with nitrogen and warmed to 90° C. Separately, 1) a monomer emulsion (A) was prepared from 556 μm of deionized water, 25 μm of sodium lauryl sulfate, 458 μm of EA, 149 μm of MAA. 2) Monomer emulsion additive (B) was prepared by mixing 5.3 μm of TMPTA and 93 g of MAA. 3) Initiator solution C1 was prepared by dissolving 0.4 μm of ammonium persulfate in 19 μm of deionized water. 4) Initiator solution C2 was prepared by dissolving 0.7 μm of ammonium persulfate in 42 μm of deionized water. At −90° C. reactor temperature, the reactor was charged with initiator solution C1. Then monomer emulsion (A) was charged into reactor while Monomer emulsion additive (B) was charged simultaneously to monomer emulsion (A). The rate was controlled so that the both feeds finished in 120 min. Separately, Initiator solution C2 was fed into the reactor in 120 min. After these additions were completed, the monomer emulsion and initiator feed lines were rinsed with deionized water followed with monomer chasing with free radical catalyst and activator. The resulting latex was filtered and analyzed for % solids, pH, residual monomer, particle size, gel content and viscosity.
To a 3-liter, 4-necked round bottom flask equipped with a mechanical stirrer, thermocouple, condenser and nitrogen sparge was added 350 μm of deionized water and 2 μm of sodium lauryl sulfate. The reactor was purged with nitrogen and warmed to 90° C. Separately, 1) a monomer emulsion (A) was prepared from 935 μm of deionized water, 25 μm of sodium lauryl sulfate, 457 μm of EA, 242 μm of MAA and 5.3 μm of TMPTA. 3) Initiator solution C1 was prepared by dissolving 0.4 μm of ammonium persulfate in 19 μm of deionized water. 4) Initiator solution C2 was prepared by dissolving 0.7 μm of ammonium persulfate in 42 μm of deionized water. At −90° C. reactor temperature, the reactor was charged with initiator solution C1. Then monomer emulsion (A) was charged into reactor. The rate was controlled so that the feed finished in 120 min. Separately, Initiator solution C2 was fed into the reactor in 120 min. After these additions were completed, the monomer emulsion and initiator feed lines were rinsed with deionized water followed with monomer chasing with free radical catalyst and activator. The resulting latex was filtered and analyzed for % solids, pH, residual monomer, particle size, gel content and viscosity.
Polymer samples 2-12 were prepared according to the procedure as described in Example 1 except the composition changes as described in Table 1.
To a 3-liter, 4-necked round bottom flask equipped with a mechanical stirrer, thermocouple, condenser and nitrogen sparge was added 545 μm of deionized water and 2 μm of sodium lauryl sulfate. The reactor was purged with nitrogen and warmed to 90° C. Separately, 1) a monomer emulsion (A) was prepared from 556 μm of deionized water, 25 μm of sodium lauryl sulfate, 458 μm of EA, 149 μm of MAA and 5.3 μm of TMPTA. 2) Monomer emulsion additive (B) was prepared by mixing 93 g of MAA and 19 μm of deionized water. 3) Initiator solution C1 was prepared by dissolving 0.4 μm of ammonium persulfate in 19 μm of deionized water. 4) Initiator solution C2 was prepared by dissolving 0.7 μm of ammonium persulfate in 42 μm of deionized water. At −90° C. reactor temperature, the reactor was charged with initiator solution C1. Then monomer emulsion (A) was charged into reactor while Monomer emulsion additive (B) was charged simultaneously to monomer emulsion (A). The rate was controlled so that the both feeds finished in 120 min. Separately, Initiator solution C2 was fed into the reactor in 120 min. After these additions were completed, the monomer emulsion and initiator feed lines were rinsed with deionized water followed with monomer chasing with free radical catalyst and activator. The resulting latex was filtered and analyzed for % solids, pH, residual monomer, particle size, gel content and viscosity.
Prepared according to the procedure as described in Example 1 except the composition changes as described in Table 1.
TABLE 1
Polymers from Examples (E) made with power feed of cross-linker
and 38% of total MAA and from a Comparative Example (CE)
made by conventional polymerization
Polymer
Polymer composition
E 1
65EA/35MAA//0.75% TMPTA
CE 1
65EA/35MAA//0.75% TMPTA
E 2
65EA/5EHA/35MAA//0.75% TMPTA
E 3
65EA/5BA/35MAA//0.75% TMPTA
E 4
65EA/35MAA//0.56% TMPTA
E 5
65EA/35MAA//0.94% TMPTA
E 6
64EA/1 Lipo-1/35MAA//0.75% TMPTA
E 7
64EA/1 Lipo-2/35MAA//0.75% TMPTA
E 8
64.5EA/0.5 Lipo-2/35MAA//0.75% TMPTA
E 9
62.5EA/2.5 MPEG750/35MAA//0.75% TMPTA
E 10
60EA/5 MPEG750/35MAA//0.75% TMPTA
E 11
65EA/35MAA//1.25% TMPTMA
E 12
65EA/35MAA//0.1% TMPDAE
E13
65EA/35MAA//0.75% TMPTA
Procedure for measuring the aqueous neutralized solution properties (viscosity and turbidity) as summarized in Table 2
Solublized viscosity procedure for 1% polymer active:
Solublized viscosity procedure for 2.5% polymer active:
Turbidity Measurement:
TABLE 2
Aqueous neutralized solution property (viscosity and turbidity) of
Polymer samples 1-13 and Comparative examples 1.
aqueous neutralized
aqueous neutralized solution
solution
property with 2.5% polymer
property with 1% polymer
viscosity
turbidity
viscosity
turbidity
Polymer
(cps, 30 rpm)
(NTU)
(cps, 30 rpm)
(NTU)
E 1
7960
30.1
2460
2.85
CE 1
3132
16.5
1340
19.4
E 2
7920
29.7
3820
4.3
E 3
7880
47.30
3860
2.86
E 4
6420
22
2280
2.2
E 5
8260
23.10
3920
3.21
E 6
9100
35.30
3540
2.62
E 7
9720
7.38
4620
3.87
E 8
6360
16.50
3460
2.89
E 9
9960
14.7
4400
3.28
E 10
8820
18.10
4660
3.64
E 11
5180
21.2
1116
1.54
E 12
7280
23.0
1908
1.42
13
9000
10.1
4740
6.8
Overall, polymer examples 1-13 gave a much higher aqueous solution viscosity than the corresponding comparative example 1.
A. Procedure for Preparation of Personal Care Formulations:
B. Formulation Variable Parameters:
SL-2EO-S
SL-1EO-S
CAPB
Ratio
Formulation 5
12.5
2.5
5/1
Formulation 13
6.25
6.25
2.5
5/1
Formulation 9
8.3
1.7
4.9/1
Formulation 10
11
4
2.75/1
Formulation 12
16.5
3.5
4.7/1
C. Viscosity Measurements
Rheology analyses were conducted using two different equipments:
D. Clarity Evaluations
Clarity was assessed using two different techniques:
E. Suspending Properties Evaluation
Suspension was evaluated in different ways:
F. Miscellaneous:
TABLE 3
Personal care formulation properties (zero-stress viscosity, turbidity)
of various polymer examples at pH of 5 and 6.5.
Zero Stress
Abs
Abs
Polymer
pH
Viscosity
NTU
(320 mm)
(400 nm)
1
5
90540
19.5
0.285
0.152
6.5
15400
16.2
0.278
0.142
CE1
5
56840
115.6
6.5
5083
5.8
2
5
21.2
0.364
0.195
6.5
10.7
0.262
0.115
3
5
246300
27.3
0.395
0.206
6.5
14.2
0.314
0.139
4
5
88130
16.7
0.288
0.133
6.5
27100
17.7
0.282
0.127
5
5
873000
56.5
0.872
0.602
6.5
185800
39.4
0.404
0.243
6
5
198000
21.8
0.341
0.166
6.5
16510
21.6
0.350
0.169
13
5
266600
67.3
0.897
0.644
6.5
135400
23.7
0.309
0.181
Overall, in comparison with comparative example 1 in personal care formulation, polymer examples 1-13 lead to a higher zero stress viscosity at both pHs.
Measurement of Glass Transition Temperature.
Glass transition temperatures (Tg) were measured using TA instruments model 2920 Differential Scanning calorimeter either with conventional (20° C./min ramp rate) or modulated temperature ramp test method.
TABLE 4
Glass transition temperature of polymer examples
Polymer sample
Glass transition temperature
Comparative
Narrow heat transition (Tg) from 55° C. to 90° C.
example 1
Polymer example 13
Broad heat transition (Tg) from 31° C. to 120° C.
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